Compound, anti-reflective film comprising same, and display device

ABSTRACT

Provided are a compound expressed by a particular chemical formula, an anti-reflective film, and a display device including the anti-reflective film.

TECHNICAL FIELD

This disclosure relates to a compound, an anti-reflective film includingthe same, and a display device including the anti-reflective film.

BACKGROUND ART

In a typical liquid crystal display (LCD), light emitted from a whitelight source passes through an RGB color filter of each pixel to form asub-pixel of each color, and a color in the RGB range may be produced bycombining these.

In recent years, new displays using light emitting bodies such asquantum dots and organic-inorganic phosphors that emit the color of eachsub-pixel are being developed and a method of using a UV light sourceand a method of using a blue light source have been proposed as methodsof excitation of these blue, green, and red light sources.

When a UV light source is used, each color is generated and implementedwith blue, green, and red light emitting bodies, but when a blue lightsource is used, green and red are each color generated by light emittingbodies, and blue pixels transmit the light source as it is.

In the case of a display material including quantum dots recentlycommercialized or under development, light emission of green quantumdots and red quantum dots through a blue light source or a white lightsource is used. Quantum dot-containing display devices are intended toimprove color gamut and luminance by using a quantum dot material, anddevelopment of a panel using quantum dot light emission using varioustypes of light sources has been continuously made. In addition, it ispossible to improve a viewing angle according to the location of thequantum dot material in a panel configuration. Next-generation quantumdot display devices are being developed in terms of increasing anintensity of a light source or in terms of developing a light sourcewith an extended blue area in order to improve luminous efficiency ofthe quantum dots.

In a quantum dot display device, a spectrum of the light source reachingthe quantum dot material has a very close effect on the efficiency ofthe quantum dot. Since characteristics of each light source aredifferent depending on the type of light source, efforts in variousfields are being continued to introduce a new approach in order toimprove efficiency of each light source.

On the other hand, in the case of a new display using a light emittingbody, it is necessary to lower a reflectance by external light or adjusta panel color caused by scattered reflection. In order to solve thisproblem, there has been an attempt to use a dye in the optical memberconstituting the panel. When a quantum dot is used as the light emittingbody, it is difficult to decrease the reflectance by external light orto adjust the panel color.

Accordingly, in the case of new displays, anti-reflective films withimprovement of luminance loss or color correction are being introduced,and recently, there are attempts to additionally apply cyanine-baseddyes or azo-based dyes as dyes capable of absorbing light of a specificwavelength to maximize the low-reflection characteristics of theanti-reflective film.

However, the cyanine-based dye or azo-based dye is capable of absorbinglight in a short wavelength region, but has a problem of lowering lightresistance reliability, and thus it is difficult to apply it to ananti-reflective film.

DISCLOSURE Technical Problem

An object of the present invention is to provide a compound capable ofabsorbing light in a red wavelength region of a light source.

Another embodiment provides an anti-reflective film including thecompound.

Another embodiment provides a display device including theanti-reflective film.

Another object of the present invention is to provide an optical memberhaving a high color correction effect and remarkably loweringreflectance to improve reflected color and to have high total lighttransmittance.

Technical Solution

An embodiment provides a compound represented by Chemical Formula 1.

In Chemical Formula 1,

M is two hydrogen atoms, a divalent metal atom, a trivalent substitutedmetal atom, a tetravalent substituted metal atom, a metal hydroxideatom, or a metal oxide atom,

R¹ to R¹⁶ are each independently hydrogen, a substituted orunsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 arylgroup, a substituted or unsubstituted C2 to C20 heteroaryl group, asulfonylamide group represented by Chemical Formula 2, or a combinationthereof, and

at least one of R¹ to R⁸ and at least one of R⁹ to R¹⁶ is asulfonylamide group represented by Chemical Formula 2.

In Chemical Formula 2,

R¹⁷ and R¹⁸ are each independently hydrogen, a substituted orunsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 arylgroup, or a substituted or unsubstituted C2 to C20 heteroaryl group,

at least one of R¹⁷ and R¹⁸ is a C3 to C20 cycloalkyl group, and

* indicates a moiety bonded to the benzene ring of Chemical Formula 1.

R¹⁷ and R¹⁸ may each independently be hydrogen or a substituted orunsubstituted C3 to C20 cycloalkyl group, and at least one of R¹⁷ andR¹⁸ may be a C3 to C20 cycloalkyl group.

M may be Cu, Co, Zn, V(═O), or Ag.

At least one of R¹ to R⁴ may be the sulfonylamide group represented byChemical Formula 2, at least one of R⁵ to R⁸ may be the sulfonylamidegroup represented by Chemical Formula 2, at least one of R⁹ to R¹² maybe the sulfonylamide group represented by Chemical Formula 2, and atleast one of R¹³ to R¹⁶ may be the sulfonylamide group represented byChemical Formula 2.

At least one of R¹ to R⁴ may be the sulfonylamide group represented byFormula 2 and the remainder may be a hydrogen atom; at least one of R⁵to R⁸ may be the sulfonylamide group represented by Chemical Formula 2and the remainder may be a hydrogen atom; at least one of R⁹ to R¹² maybe the sulfonylamide group represented by Chemical Formula 2 and theremainder may be a hydrogen atom; and at least one of R¹³ to R¹⁶ may bethe sulfonylamide group represented by Chemical Formula 2 and theremainder may be a hydrogen atom.

The compound may be a compound represented by Chemical Formula 3.

In Chemical Formula 3,

M is Cu, Co, Zn, V(═O), or Ag,

n₁ to n₄ are each independently an integer of 0 or 1, and

n₅ is an integer of 1 to 4,

provided that n₁+n₂+n₃+n₄≠0.

The compound may include a compound represented by any one ChemicalFormula 4 to Chemical Formula 14.

The compound may be a red absorbing dye.

The dye may have a maximum absorption peak at a wavelength of 650 nm to750 nm.

Another embodiment provides an anti-reflective film including thecompound.

The anti-reflective film may include an adhesive layer and ananti-reflective layer on the adhesive layer, and the compound may beincluded in the adhesive layer.

The anti-reflective film may include an adhesive layer, a dye-containinglayer, and an anti-reflective layer on the dye-containing layer, and thecompound may be included in the dye-containing layer.

Another embodiment provides a display device including theanti-reflective film.

The display device may further include a quantum dot-containing layer.

The display device may further include a quantum dot-containing layer, alight source, a color filter, and a substrate.

In the display device, the quantum dot-containing layer may be disposedon the light source, the color filter may be disposed on the quantumdot-containing layer, the substrate may be disposed on the color filter,and the anti-reflective film may be disposed on the substrate.

The substrate may include a glass substrate.

Other embodiments of the present invention are included in the followingdetailed description.

Advantageous Effects

The compound according to an embodiment is included in theanti-reflective film to absorb the light source in a near-infrared (650nm to 750 nm) region, so that even a very small amount may block thenear-infrared region to lower a reflectance of the display device due toexternal light and to improve light resistance reliability as well as toimprove luminance loss and a color gamut.

DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 are schematic views each independently illustrating ananti-reflective film according to an embodiment.

FIGS. 3 and 4 are schematic views each independently illustrating adisplay device according to an embodiment.

FIG. 5 is a graph showing the light transmittance according to thewavelength of the dyes according to Synthesis Example 1 and ComparativeExample 2.

MODE FOR INVENTION

Hereinafter, embodiments of the present invention are described indetail. However, these embodiments are exemplary, the present inventionis not limited thereto and the present invention is defined by the scopeof claims.

In the present specification, when specific definition is not otherwiseprovided, “substituted” refers to replacement of at least one hydrogenof a compound by a substituent selected from a halogen atom (F, Cl, Br,or I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyanogroup, amine group, imino group, an azido group, an amidino group, ahydrazino group, a hydrazono group, a carbonyl group, a carbamyl group,a thiol group, an ester group, ether group, a carboxyl group or a saltthereof, sulfonic acid group or a salt thereof, phosphoric acid or asalt thereof, C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 toC20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group,a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 toC20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2to C20 heterocycloalkynyl group, or a combination thereof.

In the present specification, when specific definition is not otherwiseprovided, “heterocycloalkyl group,” “heterocycloalkenyl group,”“heterocycloalkynyl group,” and “heterocycloalkylene group” refer tocycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkyl including at leastone heteroatom of N, O, S, or P in the ring compound, respectively.

In the present specification, when specific definition is not otherwiseprovided, the term “combination” refers to mixing or copolymerization.

In the present specification, when a definition is not otherwiseprovided, hydrogen is bonded at the position when a chemical bond inchemical formulae is not drawn where supposed to be given.

In the present specification, when specific definition is not otherwiseprovided, “(meth)acrylate” refers to both “acrylate” and “methacrylate,”and “(meth)acrylic acid” refers to “acrylic acid” and “methacrylicacid.”

In the present specification, when specific definition is not otherwiseprovided, “alkyl group” refers to a C1 to C20 alkyl group, andspecifically a C1 to C15 alkyl group, “cycloalkyl group” refers to a C3to C20 cycloalkyl group, and specifically a C3 to C18 cycloalkyl group,“alkoxy group” refers to a C1 to C20 alkoxy group, and specifically a C1to C18 alkoxy group, “aryl group” refers to a C6 to C20 aryl group, andspecifically a C6 to C18 aryl group, “alkenyl group” refers to a C2 toC20 alkenyl group, and specifically a C2 to C18 alkenyl group, “alkylenegroup” refers to a C1 to C20 alkylene group, and specifically a C1 toC18 alkylene group, and “arylene group” refers to a C6 to C20 arylenegroup, and specifically a C6 to C16 arylene group.

In the present specification, when a definition is not otherwiseprovided, “*” refers to a linking part between the same or differentatoms, or Chemical Formulae.

In the present specification, a “maximum absorption wavelength(λ_(max))” of a compound (dye) refers to a wavelength at which themaximum absorbance appears when absorbance is measured for a solution ofa compound (dye) at a concentration of 10 ppm in cyclohexanone. Themaximum absorbance may be measured according to a method known to thoseskilled in the art.

In the present specification, “light resistance reliability” isevaluated by a change of light transmittance. The light transmittance ofa display device is measured at a maximum absorption wavelength of a dyebefore and after irradiation under the conditions of in the Xenon TestChamber (Q-SUN) [light source lamp: Xenon lamp, irradiation intensity:0.35 W/cm², irradiation temperature: 63° C., irradiation time: 500hours, and irradiation direction: irradiation from the anti-reflectivefilm side].

An embodiment provides a compound represented by Chemical Formula 1.

In Chemical Formula 1,

M is Zn, Co, or Cu,

R¹ to R¹⁶ are each independently hydrogen, a substituted orunsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 arylgroup, a substituted or unsubstituted C2 to C20 heteroaryl group, asulfonylamide group represented by Chemical Formula 2, or a combinationthereof, and

at least one of R¹ to R⁸ and at least one of R⁹ to R¹⁶ is asulfonylamide group represented by Chemical Formula 2,

wherein, in Chemical Formula 2,

R¹⁷ and R¹⁸ are each independently hydrogen, a substituted orunsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 arylgroup, or a substituted or unsubstituted C2 to C20 heteroaryl group,wherein at least one of R¹⁷ and R¹⁸ is a C3 to C20 cycloalkyl group,and * indicates a moiety bonded to the benzene ring of Chemical Formula1.

When a near-infrared blocking dye (general Zn-PC dye) conventionallyused in a plasma display is applied to an anti-reflective film, anamount of the dye is increased to achieve a color correction function,but the anti-reflective film using the same has a problem thattransmittance of the film is increased due to discoloration of the dyein the evaluation of light resistance reliability.

The present invention is to apply Cu-PC (phthalocyanine) having aspecific substituent structure to an anti-reflective film to stronglyabsorb light in a near-infrared region and simultaneously, to reduce anamount of the dye due to improved wavelength matching and resultantly,accomplish a predetermined level of reflectance and excellent lightresistance reliability due to structural characteristics of the dye.

When the compound represented by Chemical Formula 1 is used as a dye,the compound may strongly absorb light in the near-infrared, that is, ina wavelength range of 650 nm to 750 nm and thus increase colorreproducibility of the red region and improve luminance loss of a panel,compared with a method of using the near-infrared ray-blocking dye(general Zn-PC dye). When the compound represented by Chemical Formula 1according to an embodiment is applied to an anti-reflective film, lightresistance reliability may be secured.

Specifically, when the compound represented by Chemical Formula 1 isused as a dye, luminance of the blue region (450 nm to 485 nm) and thered region (625 nm to 740 nm) may be improved.

Since the compound according to an embodiment includes a substituentrepresented by Chemical Formula 2, even with a small amount thereof mayexpress a clearer color, improving luminance of a display and obtaininga display device with excellent color characteristics.

In order to achieve a similar purpose, attempts to absorb light in awavelength region of 750 nm to 850 nm by using the conventional dye havebeen made, wherein since the conventional dye is used in a relativelylarger amount, there is a problem of securing no process margin of theentire composition.

However, when the compound according to an embodiment is used as a dye,sufficient high color reproduction may be achieved with only a smallamount of the compound, which solves the problem.

R¹⁷ and R¹⁸ may each independently be hydrogen, a substituted orunsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3to C6 cycloalkyl group, a substituted or unsubstituted C6 to C14 arylgroup, or a substituted or unsubstituted C2 to C14 heteroaryl groupheteroaryl group, wherein at least one of R¹⁷ and R¹⁸ may be a C3 to C10cycloalkyl group.

R¹⁷ and R¹⁸ may each independently be hydrogen, a substituted orunsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 toC6 cycloalkyl group, a substituted or unsubstituted C6 to C10 arylgroup, or a substituted or unsubstituted C2 to C10 heteroaryl groupheteroaryl group, wherein at least one of R¹⁷ and R¹⁸ may be a C3 to C6cycloalkyl group.

R¹⁷ and R¹⁸ may each independently be hydrogen or a substituted orunsubstituted C3 to C20 cycloalkyl group wherein at least one of R¹⁷ andR¹⁸ may be a C3 to C20 cycloalkyl group.

R¹⁷ and R¹⁸ may each independently be hydrogen or a substituted orunsubstituted C3 to C10 cycloalkyl group wherein at least one of R¹⁷ andR¹⁸ may be a C3 to C10 cycloalkyl group.

R¹⁷ and R¹⁸ may each independently be hydrogen or a substituted orunsubstituted C3 to C6 cycloalkyl group wherein at least one of R¹⁷ andR¹⁸ may be a C3 to C6 cycloalkyl group.

At least one of R¹ to R⁴ may be the sulfonylamide group represented byChemical Formula 2, at least one of R⁵ to R⁸ may be the sulfonylamidegroup represented by Chemical Formula 2, at least one of R⁹ to R¹² maybe the sulfonylamide group represented by Chemical Formula 2, and atleast one of R¹³ to R¹⁶ may be the sulfonylamide group represented byChemical Formula 2.

At least one of R¹ to R⁴ may be the sulfonylamide group represented byFormula 2 and the remainder may be a hydrogen atom; at least one of R⁵to R⁸ may be the sulfonylamide group represented by Chemical Formula 2and the remainder may be a hydrogen atom; at least one of R⁹ to R¹² maybe the sulfonylamide group represented by Chemical Formula 2 and theremainder may be a hydrogen atom; and at least one of R¹³ to R¹⁶ may bethe sulfonylamide group represented by Chemical Formula 2 and theremainder may be a hydrogen atom.

The compound may be a compound represented by Chemical Formula 3.

In Chemical Formula 3,

M is Cu, Co, Zn, V(═O), or Ag,

n₁ to n₄ are each independently an integer of 0 or 1, and

n₅ is an integer of 1 to 4,

provided that n₁+n₂+n₃+n₄≠0.

Like a structure of the compound represented by Chemical Formula 3, thesulfonylamide group substituted for the benzene ring may be substitutedat a position of two α (adjacent) and β (second) carbons, wherein onecompound may be substituted with 1 to 4 sulfonylamide groups, and mostpreferably, 3 or 4 sulfonylamide groups, obtaining the most excellentlight absorption in a red wavelength region.

For example, when the compound represented by Chemical Formula 3 may besubstituted with the four sulfonylamide groups, since the sulfonylamidegroup may be substituted on the α (adjacent) or β (second) carbon of thebenzene ring, a mixture of more than five structural isomers may beproduced, and the present invention may all include the structuralisomer mixtures.

For example, the compound represented by Chemical Formula 1 may be acompound represented by any one Chemical Formula 4 to Chemical Formula14, but is not necessarily limited thereto.

In the present invention, two or more compounds of the compoundsrepresented by Chemical Formula 4 to Chemical Formula 14 may besimultaneously included as a mixture.

The compound may be a red absorbing dye.

The dye may have a maximum absorption peak at a wavelength of 650 nm to750 nm, and specifically a maximum absorption peak at a wavelength of650 nm to 700 nm. That is, when the compound is used as a dye includedin the anti-reflective film, light in the near-infrared region may bemaximally absorbed to block the spectroscopy of the region.

According to another embodiment, an adhesive composition including thecompound according to the embodiment is provided.

The adhesive composition may include the compound represented byChemical Formula 1 in an amount of 0.0001 wt % to 1 wt %, for example,0.001 wt % to 1 wt %, for example, 0.01 wt % to 1 wt %, for example, 0.1wt % to 1 wt %, for example, 0.0001 wt % to 0.5 wt %, for example, 0.001wt % to 0.5 wt %, for example, 0.01 wt % to 0.5 wt %, for example, 0.1wt % to 0.5 wt % based on the total amount of the adhesive composition.When the compound represented by Chemical Formula 1 is included in theabove content range, it is effective to improve light resistancereliability by adjusting the panel color of the display device to whichthe anti-reflective film is applied.

Another embodiment provides an anti-reflective film including thecompound.

The anti-reflective film includes an adhesive layer and ananti-reflective layer formed on the adhesive layer, and the compoundrepresented by Chemical Formula 1 may be included in the adhesive layer.

In addition, the anti-reflective film includes an adhesive layer, adye-containing layer, and an anti-reflective layer formed on thedye-containing layer, and the compound represented by Chemical Formula 1may be included in the dye-containing layer.

That is, in the stacked structure of the anti-reflective film accordingto an embodiment, the compound represented by Chemical Formula 1 may beincluded in the adhesive layer or may be included in a separatedye-containing layer. (See FIGS. 1 and 2 )

The anti-reflective layer may consist of only a low refractive layer ormay include a low refractive layer.

The low refractive layer may lower a reflectance of the anti-reflectivefilm due to a difference in refractive index between the substrateand/or the high refractive layer described later.

The low refractive layer may include a curable binder resin, a fluorineatom-containing monomer, and fine particles (e.g., hollow silica) havingan average particle diameter of 5 nm to 300 nm, and the thickness of thelow refractive layer may be 0.01 μm to 0.15 μm. The refractive index ofthe low refractive layer may be 1.20 to 1.40.

An additional function may be imparted to the anti-reflective film byfurther forming a functional coating layer on one surface of the lowrefractive layer, that is, on the upper surface of the low refractivelayer. The functional coating layer may include an anti-fingerprintlayer, an antistatic layer, a hard coating layer, an antiglare layer, abarrier layer, etc., but is not limited thereto.

The anti-reflective layer may further include a high refractive layer.

The high refractive layer is formed between the substrate to bedescribed later and the low refractive layer, and has a refractive indexbetween the substrate and the low refractive layer, thereby reducing thereflectance of the anti-reflective layer. The high refractive layer isformed directly with the substrate and the low refractive layer,respectively. The “directly formed” means that there are no other layersbetween the layer and the layer.

The high refractive layer has a thickness of 0.05 μm to 20 μm, arefractive index of 1.45 to 2, and a haze value specified in JIS-K7361is not different from the haze value of the base material or 10% or lessof the difference between the haze value of substrate, which isexcellent in transparency and is excellent in anti-reflectiveproperties.

The hard coating layer increases a hardness of the anti-reflective layerso that even if the anti-reflective layer is used on the outermostsurface of the display device, scratches may not be generated. The hardcoating layer is not necessarily provided. The hard coating layer may beomitted if a target hardness is secured in the high or low refractivelayer.

The hard coating layer may be formed between the substrate and the highrefractive layer or between the substrate and the low refractive layer.

The hard coating layer may be a cured layer formed by uniformly mixingultrafine metal oxide particles having an average particle diameter of 1nm to 30 nm and a particle size distribution range of less than or equalto ±5 nm in a cured binder. The hard coating layer may have a thicknessof 1 μm to 15 μm, and the refractive index of the hard coating layer maybe greater than or equal to 1.54.

The anti-reflective layer may have a thickness of 50 μm to 500 μm, forexample 50 μm to 300 μm, for example 50 μm to 150 μm. When theanti-reflective layer has a thickness within the above range, it may beeasily applied to a display device.

The adhesive layer may be formed on the lower surface of theanti-reflective layer to adhere an optical member such as a display to apanel or the like. As described above, the adhesive layer may include acompound (dye) represented by Chemical Formula 1.

The adhesive layer may have a glass transition temperature of −70° C. to0° C., for example −65° C. to −20° C. When the glass transitiontemperature of the adhesive layer is within the above range, adhesion tothe panel may be improved.

The adhesive layer may be a thermosetting adhesive layer or aphotocurable adhesive layer. Desirably, since the adhesive layer becomesa thermosetting adhesive layer, it is not necessary to consider theeffect of ultraviolet rays due to the absorption wavelength of thecompound (dye) represented by Chemical Formula 1, thereby facilitatingthe manufacture of the adhesive layer. The “thermosetting adhesivelayer” may include not only an adhesive layer cured through apredetermined heat treatment at 40° C. to 100° C., but also an adhesivelayer cured at room temperature (e.g., 20° C. to 30° C.).

The adhesive layer may be formed of a composition for an adhesive layerincluding an adhesive resin and a curing agent.

The type of the adhesive resin is not limited as long as it can securethe glass transition temperature of the adhesive layer. For example, theadhesive resin may be a silicone-based, urethane-based,(meth)acryl-based resin, or the like, but desirably, a (meth)acryl-basedadhesive resin may be used.

The adhesive resin may have a glass transition temperature of −70° C. to0° C., desirably −65° C. to −20° C. When the glass transitiontemperature of the adhesive resin has the above range, adhesion to thepanel may be improved.

The adhesive resin may have a weight average molecular weight of 500,000g/mol to 2,000,000 g/mol, for example 800,000 g/mol to 1,500,000 g/mol.When the weight average molecular weight of the adhesive resin has theabove range, adhesion to the panel may be improved.

The adhesive resin may include a copolymer, desirably a random copolymerof at least one of a (meth)acryl-based monomer having an alkyl group; a(meth)acryl-based monomer having a hydroxyl group; and a(meth)acryl-based monomer having an aromatic group, a (meth)acryl-basedmonomer having an alicyclic group, and a (meth)acryl-based monomerhaving a heteroalicyclic group.

The (meth)acryl-based monomer having the alkyl group may include a(meth)acrylic acid ester having an unsubstituted C1 to C10 alkyl group.Specifically, the (meth)acryl-based monomer having the alkyl group mayinclude one or more of methyl (meth)acrylate, ethyl (meth)acrylate,propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate,iso-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate,2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl(meth)acrylate, iso-octyl (meth)acrylate, nonyl (meth)acrylate, anddecyl (meth)acrylate, but is not limited thereto. These may be includedalone or in combination of two or more. The (meth)acryl-based monomerhaving the alkyl group may be included in an amount of 60 wt % to 99.99wt %, for example 60 wt % to 90 wt %, for example 80 wt % to 99.9 wt %of the monomer mixture.

The (meth)acryl-based monomer having the hydroxyl group may include oneor more of a (meth)acryl-based monomer having a C1 to C20 alkyl grouphaving at least one hydroxyl group, a (meth)acryl-based monomer having aC3 to C20 cycloalkyl group having at least one hydroxyl group, and a(meth)acryl-based monomer having a C6 to C20 aromatic group having atleast one hydroxyl group. Specifically, the (meth)acryl-based monomerhaving the hydroxyl group may include desirably a (meth)acryl-basedmonomer having a C1 to C20 alkyl group having at least one hydroxylgroup, one or more of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl (meth)acrylate,1-chloro-2-hydroxypropyl(meth)acrylate. These may be included alone orin combination of two or more. The (meth)acryl-based monomer having thehydroxyl group may be included in an amount of 0.01 wt % to 20 wt %, forexample 0.1 wt % to 10 wt % of the monomer mixture.

The (meth)acryl-based monomer having the aromatic group may include a(meth)acrylic acid ester having a C6 to C20 aryl group or a C7 to C20arylalkyl group. Specifically, the (meth)acryl-based monomer having thearomatic group may include, but is not limited to, phenyl(meth)acrylate, benzyl (meth)acrylate, and the like. The(meth)acryl-based monomer having the aromatic group may be included inan amount of 0 wt % to 50 wt %, for example 0 wt % to 20 wt % of themonomer mixture.

In the present specification, when an alicyclic group and an alkyl groupare mixed among the monomers, it is classified as a (meth)acryl-basedmonomer having an alicyclic group. The (meth)acryl-based monomer havingthe alicyclic group may be a (meth)acrylic acid ester having a C5 to C20monocyclic or heterocyclic alicyclic group and may include at least oneof cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentanyl(meth)acrylate, methylcyclohexyl(meth)acrylate, anddicyclopentenyl(meth)acrylate. The (meth)acryl-based monomer having thealicyclic group may be included in an amount of 0 wt % to 50 wt %, forexample 1 wt % to 30 wt %, or 1 wt % to 20 wt % of the monomer mixture.

The (meth)acryl-based monomer having the heteroalicyclic group mayinclude a (meth)acrylic acid ester having a C4 to C9 heteroalicyclicgroup including at least one of nitrogen, oxygen, or sulfur.Specifically, the (meth)acryl-based monomer having the heteroalicyclicgroup may include (meth)acryloylmorpholine, but is not limited thereto.The (meth)acryl-based monomer having the heteroalicyclic group may beincluded in an amount of 0 wt % to 50 wt %, for example 0 wt % to 10 wt% of the monomer mixture.

The adhesive resin may include a (meth)acryl-based copolymer of amonomer mixture including 70 wt % to 99.99 wt %, for example 90 wt % to99.5 wt % of the (meth)acryl-based monomer having the alkyl group, 0.01wt % to 30 wt %, for example 0.5 wt % to 10 wt % of the(meth)acryl-based monomer having the hydroxyl group. When each of themonomers constituting the adhesive resin has the above ranges, adhesivestrength may be easily secured.

The curing agent may include an isocyanate-based curing agent. Thecuring agent may be included in an amount of 0.01 parts by weight to 20parts by weight, for example 0.01 parts by weight to 10 parts by weight,for example 0.1 parts by weight to 4 parts by weight, based on 100 partsby weight of the adhesive resin. When the curing agent has the aboverange, the composition may be crosslinked to form an adhesive layer andto prevent a decrease in transparency and poor reliability due to itsexcessive use.

The composition may further include conventional additives such as asilane coupling agent, an antioxidant, a tackifying resin, aplasticizer, an antistatic agent, a rework agent, and a curing catalyst.The silane coupling agent may be included in an amount of 0.01 parts byweight to 20 parts by weight, for example 0.01 parts by weight to 10parts by weight, for example 0.1 parts by weight to 4 parts by weight,based on 100 parts by weight of the adhesive resin. When the silanecoupling agent has the above range, adhesion may be controlled andreliability defects may be prevented.

The composition for the adhesive layer may be a solvent-free type or mayfurther include a conventional organic solvent to increase coatingproperties.

The adhesive layer may have a thickness of 1 μm to 50 μm, for example, 5μm to 25 μm. When the adhesive layer has a thickness within the aboverange, it may be easily used in a display device.

According to another embodiment, a display device including theanti-reflective film is provided. For example, a display deviceincluding the anti-reflective film and the quantum dot-containing layermay be provided.

For example, the display device may further include a light source, acolor filter, and a substrate.

For example, the display device may have a stacked structure in whichthe quantum dot-containing layer may be disposed on the light source,the color filter may be disposed on the quantum dot-containing layer,the substrate may be disposed on the color filter, and theanti-reflective film may be disposed on the substrate. (See FIGS. 3 and4 )

For example, the light source may be a blue light source.

For example, the substrate may be a glass substrate.

Components constituting the quantum dot-containing layer may furtherinclude a binder resin, a reactive unsaturated compound, aphotopolymerization initiator, a diffusion agent, and other additives,which will be described later, in addition to the quantum dot.

The quantum dot may have a maximum fluorescence emission wavelength(fluorescence λ_(max)) in 400 nm to 500 nm of a wavelength range of 350nm to 550 nm.

The quantum dot may have a full width at half maximum (FWHM) in a rangeof 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dothas a full width at half maximum (FWHM) within the range, the quantumdot has high color purity and thus an effect on increasing colorreproducibility when used as a color material in a color filter.

The quantum dot may be an organic material, an inorganic material, or ahybrid (mixture) of the organic material and the inorganic material.

The quantum dot may each independently include a core and a shellsurrounding the core, and herein, the core and the shell may have astructure such as a core each independently including Group II-IV, GroupIII-V, and the like, a core/a shell, a core/a first shell/a secondshell, an alloy, an alloy/a shell, and the like, but are not limitedthereto.

For example, the core may include at least one material selected fromCdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP,InAs, and an alloy thereof, but is not necessarily limited thereto. Theshell surrounding the core may include at least one material selectedfrom CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and an alloythereof but is not necessarily limited thereto.

In an embodiment, since an interest in an environment has been recentlymuch increased over the whole world, and a regulation about a toxicmaterial also has been fortified, a cadmium-free light emitting material(InP/ZnS) having little low quantum efficiency (quantum yield) but beingenvironmentally-friendly instead of a light emitting material having acadmium-based core is used but not necessarily limited thereto.

The quantum dot having a core/shell structure may have an entire size(an average particle diameter) including the shell of 1 nm to 15 nm, forexample, 5 nm to 15 nm, but its structure is not particularly limited.

For example, the quantum dot may be a red quantum dot, a green quantumdot, or a combination thereof. For example, the quantum dot may includeboth green quantum dot and red quantum dot. In this case, the greenquantum dots may be included in an amount greater than that of the redquantum dots. The red quantum dot may have an average particle diameterof 10 nm to 15 nm. The green quantum dot may have an average particlediameter of 5 nm to 8 nm. Meanwhile, for the dispersion stability of thequantum dots, a dispersant may be used together. The dispersant may helpa photoconversion material such as the quantum dot uniformly dispersedin the curable composition and include a non-ionic, anionic, or cationicdispersant. Specifically, the dispersant may include polyalkylene glycolor esters thereof, polyoxy alkylene, polyhydric alcohol ester alkyleneoxide addition products, alcohol alkylene oxide addition products,sulfonate esters, sulfonate salts, carboxylate esters, carboxylatesalts, alkyl amide alkylene oxide addition products, alkyl amines andmay be used alone or as a mixture of two or more. The dispersant may beused in an amount of 0.1 wt % to 100 wt %, for example, 10 wt % to 20 wt% based on the solid content of the photoconversion material such as thequantum dots.

The quantum dots may be included in an amount of 1 to 40 parts byweight, for example, 1 to 10 parts by weight, based on 100 parts byweight of the components constituting the quantum dot-containing layer.When the quantum dot is included within the above range, the lightconversion rate is improved and the pattern characteristics anddevelopment characteristics are not impaired, so that excellentprocessability may be obtained.

The binder resin may include an acryl-based resin, an epoxy resin, or acombination thereof.

The acryl-based resin is a copolymer of a first ethylenic unsaturatedmonomer and a second ethylenic unsaturated monomer that iscopolymerizable therewith, and is a resin including at least oneacryl-based repeating unit.

The first ethylenic unsaturated monomer is an ethylenic unsaturatedmonomer including at least one carboxyl group. Examples of the monomerinclude acrylic acid, methacrylic acid, maleic acid, itaconic acid,fumaric acid, or a combination thereof.

The first ethylenic unsaturated monomer may be included in an amount of5 wt % to 50 wt %, for example, 10 wt % to 40 wt % based on the totalamount of the acryl-based binder resin.

The second ethylenic unsaturated monomer may be an aromatic vinylcompound such as styrene, α-methylstyrene, vinyl toluene,vinylbenzylmethylether, and the like; an unsaturated carboxylate estercompound such as methyl(meth)acrylate, ethyl(meth)acrylate,butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate,phenyl(meth)acrylate, and the like; an unsaturated carboxylic acid aminoalkyl ester compound such as 2-aminoethyl(meth)acrylate,2-dimethylaminoethyl(meth)acrylate, and the like; a carboxylic acidvinyl ester compound such as vinyl acetate, vinyl benzoate, and thelike; a unsaturated carboxylic acid glycidyl ester compound such asglycidyl(meth)acrylate, and the like; a vinyl cyanide compound such as(meth)acrylonitrile, and the like; a unsaturated amide compound such as(meth)acrylamide, and the like; and the like and may be used alone or asa mixture of two or more.

Specific examples of the acryl-based resin may bepolybenzylmethacrylate, a (meth)acrylic acid/benzylmethacrylatecopolymer, a (meth)acrylic acid/benzylmethacrylate/styrene copolymer, a(meth)acrylic acid/benzylmethacrylate/2-hydroxyethylmethacrylatecopolymer, a (meth)acrylicacid/benzylmethacrylate/styrene/2-hydroxyethylmethacrylate copolymer,and the like, but are not limited thereto and may be used alone or as amixture of two or more.

The acryl-based resin may have a weight average molecular weight of1,000 g/mol to 15,000 g/mol. When the acryl-based resin has a weightaverage molecular weight within the range, close-contacting propertiesto a substrate, and physical and chemical properties are improved andviscosity is appropriate.

The epoxy resin may be a thermally polymerizable monomer or oligomer,and may include a compound having a carbon-carbon unsaturated bond and acarbon-carbon cyclic bond.

The epoxy resin may further include a bisphenol A epoxy resin, abisphenol F epoxy resin, a phenol novolac epoxy resin, a cyclicaliphatic epoxy resin, and an aliphatic polyglycidyl ether, but is notnecessarily limited thereto.

Commercially available products of the compounds may be YX4000, YX4000H,YL6121H, YL6640, or YL6677 of Yuka Shell Epoxy Co., Ltd.; EOCN-102,EOCN-1035, EOCN-104S, EOCN-1020, EOCN-1025, or EOCN-1027 of NipponKayaku Co. Ltd. and EPIKOTE 180S75 of Yuka Shell Epoxy Co., Ltd.; abisphenol A epoxy resin such as EPIKOTE 1001, 1002, 1003, 1004, 1007,1009, 1010 and 828 of Yuka Shell Epoxy Co., Ltd.; a bisphenol F epoxyresin such as EPIKOTE 807 and 834 of Yuka Shell Epoxy Co., Ltd.; aphenol novolac epoxy resin such as EPIKOTE 152, 154, or 157H65 of YukaShell Epoxy Co., Ltd. and EPPN 201, 202 of Nippon Kayaku Co. Ltd.; acyclic aliphatic epoxy resin such as CY175, CY177, and CY179 ofCIBA-GEIGY A.G Corp., ERL-4234, ERL-4299, ERL-4221 and ERL-4206 ofU.C.C., Showdyne 509 of Showa Denko K.K., Araldite CY-182 of CIBA-GEIGYA.G Corp., CY-192 and CY-184, Dainippon Ink & Chemicals Inc., EPICLON200 and 400, EPIKOTE 871, 872 of Yuka Shell Epoxy Co. and EP1032H60,ED-5661, and ED-5662 of Celanese Coating Corporation; an aliphaticpolyglycidylether may be EPIKOTE 190P and 191P of Yuka Shell Epoxy Co.,EPOLITE 100MF of Kyoeisha Yushi Kagaku Kogyo Co., Ltd., EPIOL TMP ofNihon Yushi K. K., and the like.

The binder resin may be included in an amount of 1 to 40 parts byweight, for example, 5 to 20 parts by weight, based on 100 parts byweight of the components constituting the quantum dot-containing layer.When the binder resin is included within the above range, excellentsensitivity, developability, resolution, and linearity of the patternmay be obtained.

The reactive unsaturated compound may be used by mixing monomers oroligomers generally used in conventional photocurable compositions andthermosetting compositions.

The reactive unsaturated compound may be an acrylate-based compound. Forexample, at least one of ethylene glycoldiacrylate, triethyleneglycoldiacrylate, 1,4-butanedioldiacrylate, 1,6-hexanedioldiacrylate,neopentylglycoldiacrylate, pentaerythritoldiacrylate,pentaerythritoltriacrylate, dipentaerythritoldiacrylate,dipentaerythritoltriacrylate, dipentaerythritolpentaacrylate,pentaerythritolhexaacrylate, bisphenol A diacrylate,trimethylolpropanetriacrylate, novolacepoxyacrylate, ethyleneglycoldimethacrylate, diethylene glycoldimethacrylate, triethyleneglycoldimethacrylate, propylene glycoldimethacrylate,1,4-butanedioldimethacrylate, 1,6-hexanedioldimethacrylate, or a mixturethereof may be used.

The reactive unsaturated compound may be treated with acid anhydride toimprove developability.

The reactive unsaturated compound may be included in an amount of 1 to10 parts by weight, for example, 1 to 5 parts by weight, based on 100parts by weight of the component constituting the quantum dot-containinglayer. When the reactive unsaturated compound is included within theabove range, curing occurs sufficiently during exposure in the patternformation process, resulting in excellent reliability, heat resistance,light resistance, chemical resistance, resolution, and close-contactingproperties of the pattern.

The photopolymerization initiator may be a acetophenone-based compound,a benzophenone-based compound, a thioxanthone-based compound, abenzoin-based compound, an oxime-based compound, and the like.

Examples of the acetophenone-based compound may be 2,2′-diethoxyacetophenone, 2,2′-dibutoxy acetophenone,2-hydroxy-2-methylpropinophenone, p-t-butyltrichloro acetophenone,p-t-butyldichloro acetophenone, 4-chloro acetophenone,2,2′-dichloro-4-phenoxy acetophenone,2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and thelike.

Examples of the benzophenone-based compound may be benzophenone, benzoylbenzoate, benzoyl methyl benzoate, 4-phenyl benzophenone,hydroxybenzophenone, acrylated benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4,4′-dimethylaminobenzophenone, 4,4′-di chlorobenzophenone, 3,3′-dimethyl methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound may be thioxanthone,2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone,2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, and the like.

Examples of the benzoin-based compound may be benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutylether, benzyldimethylketal, and the like.

Examples of the triazine-based compound may be2,4,6-trichloro-s-triazine,2-phenyl-4,6-bis(trichloromethyl)-s-triazine,2-(3′,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(4′-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine,2-biphenyl-4,6-bis(trichloromethyl)-s-triazine,bis(trichloromethyl)-6-styryl-s-triazine,2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-4-bis(trichloromethyl)-6-piperonyl-s-triazine,2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

Examples of the oxime-based compound may be O-acyloxime-based compound,2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione,1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Specificexamples of the O-acyloxime-based compound may be 1,2-octanedione,2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one,1-(4-phenylsulfanyl phenyl)-butane-1,2-dione-2-oxime-O-benzoate,1-(4-phenylsulfanyl phenyl)-octane-1,2-dione-2-oxime-O-benzoate,1-(4-phenylsulfanyl phenyl)-octan-1-oneoxime-O-acetate,1-(4-phenylsulfanyl phenyl)-butan-1-oneoxime-O-acetate, and the like.

The photopolymerization initiator may further include a carbazole-basedcompound, a diketone-based compound, a sulfonium borate-based compound,a diazo-based compound, an imidazole-based compound, a biimidazole-basedcompound, a fluorene-based compound, and the like, besides thecompounds.

The photopolymerization initiator may be used with a photosensitizercapable of causing a chemical reaction by absorbing light and becomingexcited and then, transferring its energy.

Examples of the photosensitizer may be tetraethylene glycolbis-3-mercapto propionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercapto propionate, and thelike.

The photopolymerization initiator may be included in an amount of 0.1parts by weight to 10 parts by weight, for example, 0.1 parts by weightto 5 parts by weight, based on 100 parts by weight of the componentsconstituting the quantum dot-containing layer. When thephotopolymerization initiator is included within the above range, abalance between sensitivity and developability during exposure isimproved, so that a pattern having excellent resolution without residualfilm may be obtained.

The quantum dot-containing layer may further include a diffusion agent.

For example, the diffusion agent may include barium sulfate (BaSO₄),calcium carbonate (CaCO₃), titanium dioxide (TiO₂), zirconia (ZrO₂), ora combination thereof.

The diffusion agent reflects light not absorbed in the aforementionedquantum dot, so that the reflected light may be adsorbed again in thequantum dot. In other words, the diffusion agent increases an amount ofthe light absorbed in the quantum dot and thus light conversionefficiency of the curable composition.

The diffusion agent may have an average particle diameter (D₅₀) within arange of 150 nm to 250 nm and specifically, 180 nm to 230 nm. When thediffusion agent has an average particle diameter within the range, muchmore excellent light scattering effects may be obtained, and lightconversion efficiency may be increased.

The diffusion agent may be included in an amount of 0.1 wt % to 20 wt %,for example 0.1 wt % to 5 wt %, based on a solid content of 100 parts byweight of components constituting the quantum dot-containing layer. Whenthe diffusion agent is included in an amount of less than 0.1 wt % basedon 100 parts by weight of components constituting the quantumdot-containing layer, it is difficult to expect the effect of improvingthe light conversion efficiency by using the diffusion agent, while whenthe diffusion agent is included in an amount of greater than 5 wt %,pattern characteristics of may be deteriorated.

In order to improve the stability and dispersibility of the quantumdots, the quantum dot-containing layer may further include a thiol-basedadditive.

The thiol-based additive may replace the shell surface of the quantumdot, and may improve dispersion stability of a quantum dot in a solventand may stabilize the quantum dot.

The thiol-based additive may have one or more, for example, 2 to 10, forexample 2 to 4 thiol groups (—SH) at the terminal end according to itsstructure.

For example, the thiol-based additive may include at least twofunctional groups represented by Chemical Formula 15.

In Chemical Formula 15,

L⁷ and L⁸ are each independently a single bond, a substituted orunsubstituted C1 to C20 alkylene group, a substituted or unsubstitutedC3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20arylene group, or a substituted or unsubstituted C2 to C20 heteroarylenegroup.

For example, the thiol-based additive may be represented by ChemicalFormula 16.

In Chemical Formula 16,

L⁷ and L⁸ are each independently a single bond, a substituted orunsubstituted C1 to C20 alkylene group, a substituted or unsubstitutedC3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20arylene group, or a substituted or unsubstituted C2 to C20 heteroarylenegroup, and

u1 and u2 are each independently an integer of 0 or 1.

For example, in Chemical Formula 15 and Chemical Formula 16, L⁷ and L⁸may each independently be a single bond or a substituted orunsubstituted C1 to C20 alkylene group. Specific examples of thethiol-based additive may be selected from pentaerythritoltetrakis(3-mercaptopropionate) represented by Chemical Formula 16a,trimethylolpropane tris(3-mercaptopropionate) represented by ChemicalFormula 16b, pentaerythritol tetrakis(mercaptoacetate) represented byChemical Formula 16c, trimethylolpropane tris(2-mercaptoacetate)represented by Chemical Formula 16d, glycol di-3-mercaptopropionaterepresented by Chemical Formula 16e, and a combination thereof.

The thiol-based additive may be included in an amount of 0.1 parts byweight to 10 parts by weight, for example 0.1 parts by weight to 5 partsby weight based on 100 parts by weight of components constituting thequantum dot-containing layer. When the thiol-based additive is includedwithin the ranges, stability of a photoconversion material such as aquantum dot may be improved, the thiol group in the component reactswith an acrylic group of a resin or a monomer to form a covalent bondand thereby heat resistance of a photoconversion material such as aquantum dot may be improved.

The quantum dot-containing layer may further include a polymerizationinhibitor including a hydroquinone-based compound, a catechol-basedcompound, or a combination thereof. As the quantum dot-containing layerfurther includes the hydroquinone-based compound, catechol-basedcompound, or combination thereof, after printing (coating) a compositionincluding quantum dots, crosslinking at room temperature may beprevented during exposure.

For example, the hydroquinone-based compound, catechol-based compound,or combination thereof may include hydroquinone, methyl hydroquinone,methoxyhydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone,2,5-bis(1,1-dimethylbutyl) hydroquinone,2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butylcatechol, 4-methoxyphenol, pyrogallol, 2,6-di-t-butyl-4-methylphenol,2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O′) aluminium, or acombination thereof, but is not necessarily limited thereto.

The hydroquinone-based compound, catechol-based compound, or combinationthereof may be used in the form of a dispersion, and the polymerizationinhibitor in the dispersion form may be included in an amount of 0.001parts by weight to 1 part by weight, for example 0.01 parts by weight to0.1 parts by weight, based on 100 weight of components constituting alayer including a quantum dot and a fluorescent dye or a quantumdot-containing layer (including no fluorescent dye). When the stabilizeris included within the above range, the problem with aging at roomtemperature may be solved and sensitivity reduction and surface peelingmay be prevented.

The quantum dot-containing layer may further include malonic acid;3-amino-1,2-propanediol; a silane-based coupling agent; a levelingagent; a fluorine-based surfactant; or combination thereof in additionto the thiol-based additive and polymerization inhibitor.

In addition, the quantum dot-containing layer may further include asilane coupling agent having a reactive substituent such as a carboxylgroup, a methacryloyl group, an isocyanate group, an epoxy group, andthe like to improve its close-contacting properties to a substrate.

Examples of the silane-based coupling agent may include trimethoxysilylbenzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxy propyl trimethoxysilane,β-epoxycyclohexyl)ethyltrimethoxysilane, and the like and these may beused alone or in a mixture of two or more.

The silane-coupling agent may be included in an amount of 0.01 parts byweight to 10 parts by weight based on 100 parts by weight of componentsconstituting the quantum dot-containing layer. When the silane-couplingagent is included within the range, close contacting property, storingproperty, and the like may be improved.

In addition, the quantum dot-containing layer may further include asurfactant, for example a fluorine-based surfactant to improve coatingand prevent a defect if necessary.

Examples of the fluorine-based surfactant may be BM-1000® and BM-1100®of BM Chemie Inc.; MEGAFACE F 142D®, F 172®, F 173, and F 183 ofDainippon Ink Kagaku Kogyo Co., Ltd.; FULORAD FC-135®, FULORAD FC-170C®,FULORAD FC-430°, and FULORAD FC-431 of Sumitomo 3M Co., Ltd.; SURFLON5-112®, SURFLON 5-113®, SURFLON S-131®, SURFLON S-141®, and SURFLONS-145® of ASAHI Glass Co., Ltd.; and SH-28PA®, SH-190®, SH-193®,SZ-6032®, and SF-8428®, and the like of Toray Silicone Co., Ltd.; F-482,F-484, F-478, F-554 and the like of DIC Co., Ltd.

The fluorine-based surfactant may be included in an amount of 0.001parts by weight to 5 parts by weight based on 100 parts by weight ofcomponents constituting the quantum dot-containing layer. When thefluorine-based surfactant is included within the range, excellentwetting on a glass substrate as well as coating uniformity may besecured, but a stain may not be produced.

In addition, a certain amount of other additives such as antioxidantsand stabilizers may be further added to the quantum dot-containing layerwithin a range that does not impair physical properties.

A method of manufacturing each of the quantum dot-containing layers mayinclude coating a curable composition including the above-describedcomponents and the like on a substrate by an ink jet spraying method(S1) to form a pattern; and curing the pattern (S2).

(S1) Formation of Pattern

The curable composition is coated on a substrate in a thickness of 0.5to 10 μm in an ink jet dispersion method. According to the inkjetdispersion, a pattern may be formed by repetitively dispersing desiredcolors one by one or simultaneously dispersing the desired colors tosimplify the process.

(S2) Curing

A cured resin film can be obtained by curing the obtained pattern. Atthis time, a thermal curing process is preferable as a method of curing.The thermal curing process may be a process of first removing thesolvent in the curable composition by heating at a temperature ofgreater than or equal to about 100° C. for about 3 minutes, and thencuring by heating at a temperature of 160° C. to 300° C., and moredesirably heating at a temperature of 180° C. to 250° C. for about 30minutes.

In addition, each of the quantum dot-containing layers may bemanufactured without ink jetting. The manufacturing method in this caseincludes, coating the curable composition including the aforementionedcomponents, for example, at a thickness of 0.5 μm to 10 μm using asuitable method such as spin coating, roller coating, spray coating,etc. on a substrate subjected to a predetermined pretreatment, andirradiating the resultant with light to form a pattern required for thecolor filter. As a light source used for irradiation, UV, electron beam,or X-ray may be used, and for example, UV in a region of 190 nm to 450nm, specifically 200 nm to 400 nm may be irradiated. In the irradiationprocess, a photoresist mask may be further used. After performing theirradiation process in this way, the composition layer irradiated withthe light source is treated with a developing solution. At this time,the unexposed portion of the composition layer is dissolved to form apattern necessary for the color filter. By repeating this processaccording to the number of required colors, a color filter having adesired pattern may be obtained. In addition, when an image patternobtained by development in the above process is heated again or cured byirradiation with actinic rays, crack resistance and solvent resistancemay be improved.

The curable composition may further include a solvent.

The solvent may include compounds of alcohols such as methanol, ethanol,and the like; glycol ethers such as ethylene glycol methylether,ethylene glycol ethylether, propylene glycol methylether, and the like;cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolveacetate, diethyl cellosolve acetate, and the like; carbitols such asmethylethyl carbitol, diethyl carbitol, diethylene glycolmonomethylether, diethylene glycol monoethylether, diethylene glycoldimethylether, diethylene glycol methylethylether, diethylene glycoldiethylether, and the like; propylene glycol alkylether acetates such aspropylene glycol monomethylether acetate, propylene glycol propyletheracetate, and the like; ketones such as methylethylketone, cyclohexanone,4-hydroxy-4-methyl-2-pentanone, methyl-n-propylketone,methyl-n-butylketone, methyl-n-amylketone, 2-heptanone, and the like;saturated aliphatic monocarboxylic acid alkyl esters such as ethylacetate, n-butyl acetate, isobutyl acetate, and the like; lactic acidalkyl esters such as methyl lactate, ethyl lactate, and the like;hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethylhydroxyacetate, butyl hydroxyacetate, and the like; acetic acidalkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate,methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, and thelike; 3-hydroxypropionic acid alkyl esters such as methyl3-hydroxypropionate, ethyl 3-hydroxypropionate, and the like;3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate,ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl3-ethoxypropionate, and the like; 2-hydroxypropionic acid alkyl esterssuch as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl2-hydroxypropionate, and the like; 2-alkoxypropionic acid alkyl esterssuch as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl2-ethoxypropionate, methyl 2-ethoxypropionate, and the like;2-hydroxy-2-methylpropionic acid alkyl esters such as methyl2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, andthe like; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and thelike; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethylpropionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate,and the like; or ketone acid esters such as ethyl pyruvate, and thelike. In addition, N-methylformamide, N,N-dimethyl formamide,N-methylformanilide, N-methylacetamide, N,N-dimethyl acetamide,N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether,acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol,1-nonanol, benzylalcohol, benzyl acetate, ethyl benzoate, diethyloxalate, diethyl maleate, γbutyrolactone, ethylene carbonate, propylenecarbonate, phenyl cellosolve acetate, dimethyladipate may also be used,but is not limited thereto.

For example, the solvent may be desirably glycol ethers such as ethyleneglycol monoethylether, ethylenediglycolmethylethylether, and the like;ethylene glycol alkylether acetates such as ethyl cellosolve acetate,and the like; esters such as 2-hydroxy ethyl propionate, and the like;carbitols such as diethylene glycol monomethylether, and the like;propylene glycol alkylether acetates such as propylene glycolmonomethylether acetate, propylene glycol propylether acetate, and thelike; alcohols such as ethanol, and the like, or a combination thereof.

For example, the solvent may include propylene glycol monomethyletheracetate, dipropylene glycol methylether acetate, ethanol, ethyleneglycoldimethylether, ethylenediglycolmethylethylether, diethyleneglycoldimethylether, dimethyl acetamide, 2-butoxyethanol,N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate,γ-butyrolactone, dimethyladipate, or a combination thereof.

The solvent may be included in a balance amount based on a total amountof the curable composition.

Hereinafter, examples of the present invention are described. Theseexamples, however, are not in any sense to be interpreted as limitingthe scope of the invention.

(Synthesis of Compounds) Synthesis Example 1: Synthesis of CompoundRepresented by Chemical Formula 10

(1) In a 500 ml round-bottomed flask, 35 g of chlorosulfonic acid wasput and then, stirred at less than 30° C. 5 g of CuPC (copper(II)phthalocyanine) was slowly added thereto at less than or equal to 50° C.and then, stirred at 90° C. for 3 hours. The reactant was cooled againto less than 30° C., and thionyl chloride (4 g) was slowly added theretoin a dropwise fashion at less than 30° C. When the addition wascompleted, the reactant was stirred at 95° C. for 1 hour. Subsequently,the reactant was cooled to room temperature and neutralized by using 300mL of water at less than or equal to 10° C. Then, a solid therefrom wasseveral times washed with water.

(2) The filtered solid was put in a flask, and 100 mL of water was addedthereto and then, stirred and cooled to 10° C. Subsequently,cyclohexylamine (3.4 g) was slowly added thereto in a dropwise fashionand then, stirred for 1 hour. After increasing the reaction temperatureto 65° C., the mixture was reacted for 6 hours. The reactant wasfiltered and washed, and a solid produced therein was dried, obtaining53 g of a compound represented by Chemical Formula 10.

[M+H]⁺ (1222), λmax=(673) nm

Synthesis Example 2: Synthesis of Compound Represented by ChemicalFormula 17

A compound represented by Chemical Formula 17 was synthesized in thesame manner as in Synthesis Example 1 except that cyclopentylamine wasused in the cyclohexylamine.

[M+H]⁺ (1165), λmax=(673) nm

Comparative Synthesis Example 1: Synthesis of Compound Represented byChemical Formula 18

4-(2-phenylphenoxy)phthalonitrile (4 g), diazabicycloundec-7-ene (2.5g), and 40 mL of 1-pentenol were put in a 250 mL flask and then, heatedto dissolve the solids, and copper acetate (1.8 g) was added thereto andthen, refluxed, while heated. When a reaction was completed, afterremoving the solvent, the residue was purified through columnchromatography. The obtained solid was dissolved in an appropriateamount of dichloromethane thereto and then, crystallized in methanol.The obtained solid was filtered and vacuum-dried, synthesizing acompound represented by Chemical Formula 18.

[M+H]⁺ (1249), λmax=(673) nm

Comparative Synthesis Example 2: Synthesis of Compound Represented byChemical Formula 19

A compound represented by Chemical Formula 19 was synthesized in thesame manner as in Synthesis Example 1 except that 2-ethylhexylamine wasused instead of the cyclohexylamine.

[M+H]⁺ (1342), λmax=(672) nm

Comparative Synthesis Example 3: Synthesis of Compound Represented byChemical Formula 20

A compound represented by Chemical Formula 20 was synthesized in thesame manner as in Synthesis Example 1 except that methyl leucinate wasused instead of the cyclohexylamine.

[M+H]⁺ (1406), λmax=(671) nm

Preparation Example: Preparation of Copolymer of Composition forAdhesive Layer

100 parts by weight of a monomer mixture including 99 parts by weight ofn-butylacrylate and 1 part by weight of 2-hydroxyethylacrylate and 150parts by weight of ethylacetate were put into a 1 L reactor equippedwith a condenser to conveniently control a temperature, in whichnitrogen gas was refluxed, and while the flask was stirred, nitrogen gaswas injected thereinto for 1 hour to substitute nitrogen for oxygen inthe reactor, and then, the reactor was maintained at 70° C. 0.06 partsby weight of 2,2′-azobisisobutyronitrile as an initiator was addedthereto and then, reacted for 8 hours to prepare a solution containing a(meth)acryl-based copolymer. The (meth)acryl-based copolymer had Tg of−46° C. and a weight average molecular weight of 1,100,000 g/mol. Ethylacetate was added thereto, preparing 19.4 wt % of a (meth)acryl-basedcopolymer solution.

Example 1

The composition for a thermosetting coating layer was directly coated onthe bottom surface of a PET film, which was a base film of ananti-reflective film (the anti-reflective film in which a hard coatinglayer, a high refractive layer, and a low refractive layer weresequentially laminated on the top surface of the PET film as a basefilm, Reflectance: 0.2%, DNP, LLC.) with a bar coater and then, dried ina 90° C. oven for 4 minutes, manufacturing a sheet for an optical memberincluding a 20 μm-thick thermosetting coating layer.

Based on 100 parts by weight of the (meth)acryl-based copolymer preparedin the preparation example, 0.193 parts by weight of an XDI-basedisocyanate-based crosslinking agent (Solid: 75%, TD-75, Soken Chemical &Engineering Co., Ltd.) and 0.154 parts by weight of 3-glycidoxypropyltrimethoxysilane (KBM-403, ShinEtsu Chemical Co., Ltd.) as a silanecoupling agent were mixed. As a selective wavelength absorption dye,0.06 parts by weight of the compound of Synthesis Example 1 (representedby Chemical Formula 10) and 25 parts by weight of methylethylketone wereadded thereto, preparing a composition for an adhesive layer. Thecomposition for an adhesive layer was applied to a PET release film anddried in a 90° C. oven for 4 minutes, manufacturing a 20 μm-thickadhesive sheet.

The obtained adhesive sheet was laminated on the bottom surface of thePET film, which was a base film of an anti-reflective film (theanti-reflective film in which a hard coating layer, a high refractivelayer, and a low refractive layer were sequentially laminated on the topsurface of the PET film as a base film, Reflectance: 0.2%, DNP, LLC.),manufacturing an optical member of Example 1 in which the release film,the adhesive layer, and the anti-reflective film were sequentiallylaminated.

Example 2

An optical member was manufactured in the same manner as in Example 1except that the compound (represented by Chemical Formula 17) ofSynthesis Example 2 was used instead of the compound (represented byChemical Formula 10) of Synthesis Example 1.

Comparative Example 1

An optical member was manufactured in the same manner as in Example 1except that the compound (represented by Chemical Formula 18) ofComparative Synthesis Example 1 was used instead of the compound(represented by Chemical Formula 10) of Synthesis Example 1.

Comparative Example 2

An optical member was manufactured in the same manner as in Example 1except that phthalocyanine-based dye (Maximum absorption wavelength: 752nm, IN-88, Ukseung Chemical Co., Ltd.) was used instead of the compound(represented by Chemical Formula 10) of Synthesis Example 1.

Comparative Example 3

An optical member was manufactured in the same manner as in Example 1except that the compound (represented by Chemical Formula 19) ofComparative Synthesis Example 2 was used instead of the compound(represented by Chemical Formula 10) of Synthesis Example 1.

Comparative Example 4

An optical member was manufactured in the same manner as in Example 1except that the compound (represented by Chemical Formula 20) ofComparative Synthesis Example 3 was used instead of the compound(represented by Chemical Formula 10) of Synthesis Example 1.

Evaluation 1: Transmittance

The transmittances of the optical members according to Example 1 andComparative Example 2 were measured at each wavelength using a UV-visspectrophotometer, and the results are shown in Table 1.

TABLE 1 Transmittance for each wavelength @460 nm (Blue) @630 nm (Red)@673 nm Example 1 99.8% 94.9% 67.0% Comparative 86.5% 91.5% 67.1%Example 2

Referring to Table 1, the optical member of Example 1 and the opticalmember of Comparative Example 2 equally absorbed light in a region of673 nm and exhibited almost the same transmittance in a region of 460 nmand 630 nm, but the optical member of Example 1 exhibited highertransmittance than that of Comparative Example 2 and thus improvedluminescence characteristics in the corresponding region.

Evaluation 2: Light Resistance Reliability

In order to check whether or not light resistance reliability wasevaluated, the optical members according to Examples 1 and 2 andComparative Examples 1 to 4 were measured with respect to lighttransmittance at a maximum absorption wavelength of each compound underthe conditions [Light source lamp: Xenon lamp, Irradiation intensity:0.35 W/cm², Irradiation temperature: 63° C., Irradiation time: 500hours, Irradiation direction: from a side of the anti-reflective film]in Xenon Test Chamber (Q-SUN), and a change of the light transmittancewas used to evaluate the light resistance reliability, and the resultsare shown in Table 2.

TABLE 2 Light resistance reliability (ΔT %) Example 1 0.1 Example 2 0.1Comparative Example 1 12.1 Comparative Example 2 94.2 ComparativeExample 3 1.3 Comparative Example 4 5.4

Referring to Table 2, as in Examples 1 and 2, the anti-reflective filmsincluding a dye having a cyclic substituent exhibited excellent lightresistance reliability, compared with the anti-reflective films includedin Comparative Examples 1 to 4.

In particular, the anti-reflective film including a dye with a zincphthalocyanine structure according to Comparative Example 2 exhibitedvery weak light resistance reliability.

While this invention has been described in connection with what ispresently considered to be practical example embodiments, it is to beunderstood that the invention is not limited to the disclosedembodiments, but, on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims. Therefore, the aforementioned embodimentsshould be understood to be exemplary but not limiting the presentinvention in any way.

DESCRIPTION OF SYMBOLS

-   10 blue light source-   20 quantum dot-containing layer-   30 color filter-   40 substrate-   50 adhesive layer-   60 dye-containing layer-   70 anti-reflective layer-   80 anti-reflective film-   100 display device

1. A compound represented by Chemical Formula 1:

wherein, in Chemical Formula 1, M is two hydrogen atoms, a divalentmetal atom, a trivalent substituted metal atom, a tetravalentsubstituted metal atom, a metal hydroxide group, or a metal oxide group,R¹ to R¹⁶ are each independently hydrogen, a substituted orunsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 arylgroup, a substituted or unsubstituted C2 to C20 heteroaryl group, asulfonylamide group represented by Chemical Formula 2, or a combinationthereof, and at least one of R¹ to R⁸ is a sulfonylamide grouprepresented by Chemical Formula 2 and at least one of R⁹ to R¹⁶ is asulfonylamide group represented by Chemical Formula 2;

wherein, in Chemical Formula 2, R¹⁷ and R¹⁸ are each independentlyhydrogen, a substituted or unsubstituted C1 to C20 alkyl group, asubstituted or unsubstituted C3 to C20 cycloalkyl group, a substitutedor unsubstituted C6 to C20 aryl group, or a substituted or unsubstitutedC2 to C20 heteroaryl group, at least one of R¹⁷ and R¹⁸ is a substitutedor unsubstituted C3 to C20 cycloalkyl group, and indicates a bondinglocation to a benzene ring of Chemical Formula
 1. 2. The compound ofclaim 1, wherein: R¹⁷ and R¹⁸ are each independently hydrogen or asubstituted or unsubstituted C3 to C20 cycloalkyl group, and at leastone of R¹⁷ and R¹⁸ is a substituted or unsubstituted C3 to C20cycloalkyl group.
 3. The compound of claim 1, wherein M is Cu, Co, Zn,V(═O), or Ag.
 4. The compound of claim 1, wherein: at least one of R¹ toR⁴ is a sulfonylamide group represented by Chemical Formula 2, at leastone of R⁵ to R⁸ is a sulfonylamide group represented by Chemical Formula2, at least one of R⁹ to R¹² is a sulfonylamide group represented byChemical Formula 2, and at least one of R¹³ to R¹⁶ is a sulfonylamidegroup represented by Chemical Formula
 2. 5. The compound of claim 1,wherein: at least one of R¹ to R⁴ is a sulfonylamide group representedby Chemical Formula 2 and remaining ones of R¹ to R⁴ are each a hydrogenatom, at least one of R⁵ to R⁸ is a sulfonylamide group represented byChemical Formula 2 and remaining ones of R⁵ to R⁸ are each a hydrogenatom, at least one of R⁹ to R¹² is a sulfonylamide group represented byChemical Formula 2 and remaining ones of R⁹ to R¹² are each a hydrogenatom, and at least one of R¹³ to R¹⁶ is a sulfonylamide grouprepresented by Chemical Formula 2 and remaining ones of R¹³ to R¹⁶ areeach hydrogen atom.
 6. The compound of claim 1, wherein: the compound isrepresented by Chemical Formula 3:

in Chemical Formula 3, M is Cu, Co, Zn, V(═O), or Ag, n₁ to n₄ are eachindependently 0 or 1, and n₅ is an integer of 1 to 4, provided thatn₁+n₂+n₃+n₄≠0.
 7. The compound of claim 1, wherein the compound isrepresented by one Chemical Formula 4 to Chemical Formula 14:


8. The compound of claim 1, wherein the compound is a red absorbing dye.9. The compound of claim 8, wherein the dye has a maximum absorptionpeak at a wavelength of 650 nm to 750 nm.
 10. An anti-reflective filmcomprising the compound of claim
 1. 11. The anti-reflective film ofclaim 10, wherein the anti-reflective film includes an adhesive layerand an anti-reflective layer on the adhesive layer, and the compound isincluded in the adhesive layer.
 12. The anti-reflective film of claim10, wherein the anti-reflective film includes an adhesive layer, adye-containing layer, and an anti-reflective layer on the dye-containinglayer, and the compound is included in the dye-containing layer.
 13. Adisplay device comprising the anti-reflective film of claim
 10. 14. Thedisplay device of claim 13, further comprising a quantum dot-containinglayer.
 15. The display device of claim 14, further comprising a lightsource, a color filter, and a substrate.
 16. The display device of claim15, wherein, in the display device, the quantum dot-containing layer isdisposed on the light source, the color filter is disposed on thequantum dot-containing layer, the substrate is disposed on the colorfilter, and the anti-reflective film is disposed on the substrate. 17.The display device of claim 15, wherein the substrate includes a glasssubstrate.